Stabilization of organic substances



United States Patent 3,197,497 STABILIZATION OF ORGANIC SUBSTANQES Henryk A. Cyba, Chicago, Ill., assignor to Universal Gil Products Company, Des Plaines, 151., a corporation of Delaware No Drawing. Filed May 8, 1962, Ser. No. 193,337 9 Claims. (Cl. 252-466) This is a continuation-in-part of my co-pending and now abandoned application Serial No. 174,710, filed February 21, 1962, which, in turn, is a continuation-inpart of now abandoned application Serial No. 836,084, filed August 26, 1959, and relates to the stabilization of organic substances by incorporating therein a novel composition of matter which serves to inhibit deterioration of the organic substance during storage, transportation and/or use.

The novel composition of matter of the present invention is selected from dithiophosphatyl thioepoxyalkane and dithiophosphatyl epoxyalkane and is represented by the following formulas:

where R is hydrogen or a hydrocarbon group, R is an a-lkylene group, and R is hydrogen, a hydrocarbon group, or a dithiophosphatyl group.

In one embodiment of the invention, R is an alkyl group of 1 to carbon atoms, R is an alkylene group of 1 to 6 carbon atoms and R" is hydrogen, an alkyl group of 1 to 6 carbon atoms, or a dithiophosphatyl group. The thioepoxy or epoxy moiety is the sum of the carbon atoms in R and R and, accordingly, is from 3 to 14 carbon atoms. These compounds are named dialkyldithiophosphatyl thioepoxyalkanes and diallcyldithiophospha-tyl epoxyalkanes.

The novel compounds of the present invention are readily prepared by the reaction of an alkali metal dithiophosphate and a haloepoxide in the presence of an oxygencontaining polar solvent. It is essential that the reaction be etfected in the presence of the oxygen-containing polar solvent in order to form the novel compounds of the present invention by the inter-action of the alkali metal component of the dithiophosphate and the halogen of the haloepoxide. When using a non-polar solvent, entirely different reaction products are obtained, apparently constituting an addition type reaction in which both the alkali metal and the halogen are retained in the final product.

When reacting the alkali metal dithiophosphate with the haloepoxide, the dialkyldithiophosphatyl thioepoxyalkane and the dialkyldithiophosphatyl epoxyalkane are formed, the former generally predominating in the mixture of products. While not intending to be limited to the following explanation, applicant believes that decomposition of some of the dialkyldithiophosphate occurs under the reaction conditions to liberate sulfur which then replaces the oxygen in the epoxy group to form the thioepoxyalkane derivative. This accounts for the formation of the thioepoxyalkane derivative. However, as hereinbefore set forth, the final product also contains the epoxyalkane derivative.

3,1914%? Patented July 27, 1965 F or economic reasons, sodium or potassium is preferred as the alkali metal component, although it is understood that lithium, rubidium or cesium may be utilized in some cases. The reaction is readily efiected by refluxing the alkali metal salt of the dithiophosphate and the haloexpoxide in the presence of the oxygen-containing polar solvent.

In a preferred embodiment, epichlorohydrin is used as the haloepoxide and the resultant compounds will comprise those in which R in the above general formula is a methylene radical and R" is hydrogen. When reacted with sodium or potassium dithiophosphoric acid, R in the above general formula is hydrogen and the resultant compounds are l-Sdithiophosphatyl-2,3-thioepoxypropane and l-S-dithiophospha-tyl-2,3-epoxypropane. In a preferred embodiment, the dithiophosphatyl component preferably contains 1 0r 2 alkyl groups, each containing from about 3 to about 20 carbon atoms. Illustrative compounds formed by the reaction of epichlorohydrin with such dialkyldithiophosphates include 1-S-(0,0-dimethyl dithiophosphatyl) 2,3-thieoepoxypropane,

l-S-(0,0-dirnethyl dithiophosphaty) 2,3-epoxypropane,

l-S-(0,0-diethyl dithiophosphatyl) 2,3-thioepoxypropane,

1-S-(0,0-diethyldithiophosphatyl) 2,3-epoxypropane,

and when used in lubricating oils, higher alkyl derivatives are preferred, such as l-S-{0,0-dipropyl dithiophosphatyl) 2,3-t-hioepoxypropane,

1-S-(0,0-dipropyl dithiophosphatyl) 2,3-epoxypropane,

1-S-(0,0-dibutyl dithiophosphatyl) 2,3-thioep0xypropane,

S-(0,0-dibutyl dithiophosphatyl) 2,3-epoxypropane,

S-(0,0-diamyl dithiophosphatyl) 2,3-thioepoxypropane,

-S-(0,0-diamyl dithiophosphatyl) 2,3-epoxy-propane,

-S-(G,O-dihexyl dithiophosphatyl) 2,3-thioepoxypropane l-S-(QO-dihexyl dithiophosphatyl) 2,3-epoxypropane,

1-S-(0,0-diheptyl dithiophosphatyl) 2,3-thioepoxypropane,

1-S-(0,0-diheptyl dithiophosphatyl) 2,3-epoxypropane,

l-S(0,0-dioctyl dithiophosphatyl) 2,3 thioepoxypropane,

l-S-(0,0-dioctyl dithiophosphatyl) 2,3-epoxypropane,

1-S-(0,0-dinonyl dithiophosphatyl) 2,3-thioepoxypropane l-S-(0,0-dinonyl dithiophosphatyl) 2,3-epoxypropane,

1-S-(0,0-didecyl dithiophosphatyl( 2,*3-thioepoxypropane l-S-(0,0-didecyl dithiophosphatyl) 2,3-epoxypropane,

l-S-(QO-diundecyl dithiophosphatyl) 2,3-thioepoxypropane,

l-S-(0,0-diundecyl dithiophosphatyl) 2,3-epoxypropane,

1-S-(0,0-didodecyl dithiophosphatyl) 2,3-thioepoxypropane,

1-S-(0,0-didodecyl dithiophosphatyl) 2,3-epoxypropane,

1-S-(0,0-ditrideeyl dithiophosphatyl) 2,3-thioepoxypropane,

l-S-(0,0-ditridecyl dithiophosphatyl) 2,3-epoxypropane,

1-S-(0,0ditetradecyl dith-iophosphatyl) 2,3-thioepoxypropane,

l-S-(0,0-ditetradecyl dithiophosphatyl) 2,3-epoxypropane 1-S-(0,0-dipenthadecyl dithiophosphatyl) 2,3-thioepoxypropane,

1-S-(0,0-dipentadecyl di-thiophosphatyl) 2,3-epoxypropane,

1-S-(0,0-dihexadecyl dithiophosphatyl) 2,3-thioep0Xypropane,

I-S-(QO-dihexadecyl dithiophosphatyl) 2,3-epoxypropane,

1-S-(0,0-diheptadecy1 dithiophosphatyl) 2,3-thioepoxypropane 1-S-(0,0-diheptadecyl dithiophosphatyl) 2,3-epoxypropane,

1-S-(O,D-dioctadecyl dithiophosphatyl) 2,-3-thioepoxypropane 1-S(0,0-dioctadecyl dithiophosphatyl) 2,3-epoxypropane,

1-S-(0,0-dinonadecyl dithiophosphatyl) 2,3thioepoxypropane,

1-S(0,0-dinonadecyl dithiophosphatyl) 2,3-epoxypropane,

1-S-(0,0-dieicosyl dithiophosphatyl) 2,3-thioepxypropane,

I-S-(QO-dieicosyl dithiophosphatyl) 2,3-epoXypropane, etc.

Generally, the alkyl groups are the same as in the compounds specifically set forth above. In some cases the alkyl groups may be ditlerent as, for example, in compounds as l-s-(O-propyl-O-amyl dithiophosphatyl) 2,3-thioepoxypropane,

1-S-(O-propyl-O-amyl dithiophosphatyl) 2,3-epoxypropane,

l-S-(O-amyl-O-tridecyl dithiophosphatyl) 2,3-thioepoxypropane,

I-S-(O-amyl-O-tridecyl dithiophosphatyl) 2,3-epoxypropane, etc.

Illustrative compounds in which a monoalkylphosphate is reacted with epichlorohydrin include The alkyl group or groups may be straight or branched chain. It i understood that mixtures of the monoand dialkyl substituted compounds may be employed. In some cases, mixtures of the monoand dia-lkyldithiophosphates are available commercially, generally at a lower price, and such mixtures conveniently are used in preparing the novel compounds of the present invention.

Where R" in the above general formula is a dithiophosphatyl group, the compounds are produced by the reaction of a dihaloepoxide and alkali metal dithiophospha'te. Illustrative compounds formed by the reaction of 1,4-dichloro 2,3-epoxybutane with dialkyl dithiophosphates are 4% 1,4-bis-S-(0,0-dipropyl dithiophosphatyl) 2,3-thioepoxybutane, 1,4-bis-S-(O,O-d ipropyl clithiophosphatyl) 2,3-epoxybutane, 1,4-bis-S-(0,0dibutyl dithiophosphatyl) 2,3-thioepoxybutane,

1,4-bis-S-(0,0-dibutyl dithiophosphatyl) 2,3-epoxybutane,

1,4-bis-S-(0,0-diamyl dithiophosph-atyl) 2,3-thioepoxybutane,

1,4-bis-S(0,0-d iamyl dithiophosphatyl) 2,3-epoxybutane,

1,4-bis-S-(0,0-dihexy1 dithio-phosphatyl) 2,3-thioepoxy- :butane,

1,4-bis-S(0,0-dihexyl dithiophosphatyl) 2,3-epoxybutane,

1,4 bis-S-(O,O-dil1eptyl dithiophosphatyl) 2,3-thioepoxybutane,

1,4-bis-S-(0,0-diheptyl dithiophosphatyl) 2,3-epoxybutane,

1,4-bis-S-(0,0-dioctyl-dithiophosphatyl) 2,3-thioepoxybutane,

1,4-bis-S-(0,0-dioctyl dithiophosphatyl) 2,3-epoxybutane,

1,4-bis-S-(0,0-dinonyl dithiophosphatyl) 2,3-thioepoxybutane,

1,4-bis-S-(0,0-dinonyl dithiophosphatyl) 2,3-epoxybutane,

1, 4-bis-S-(0,0-didecyl dithiophosphatyl) 2,3-thioepoxybutane,

1,4-bis-S-(0,0-didecyl dithiophosphatyl) 2,3-epoxybutane,

1,4-bis-S-(0,0-diundecyl dithiophosphatyl) 2,3-thi0- epoxybutane,

l,4 bis-S-(0,0-diundecyl dithiophosphatyl) 2,3-epoxybutane,

1,4bis-S-(0,0-didodecyl dithiophosphatyl) 2,3-thioepoxybutane,

1,4-bis-S-(0,0-didodecyl di-thiophosphatyl) 2,3-epoxybutane,

1,4-bis-S-(0,0-ditridecy1 dithiophosphatyl) 2,3-thioepoxybutane,

1,4-bis-S-(0,0-ditridecy1 dithiophosphatyl) 2,3-epoxybutane,

1,4-bis-S-(0,0-ditetradecyl dithiophosphatyl) 2,3-thioepoxybutane,

1,4-bis-S-(0,0-ditetradecyl dithiophosphatyl) 2,3-

epoxybutane,

l,4-bis-S-(0,0-dipentadecyl dithiophosphatyl) 2,3-thioepoxybutane,

1;4+bis-S-(0,0-dipentadecy1 dithiophosphatyl) 2,3-

epoxybutane,

1,4-bis-S-(0,0-dihexadecyl dithiophosphatyl) 2,3-thioepoxybutane,

1,4-bis-S-(0,0-dihexadecyl dithiophosphatyl) 2,3-

epoxybutane,

1,4-bis-S-(0,0-diheptadecyl dithiophosphatyl) 2,3-thioepoxybutane,

1,4-bis-S (O,O-diheptade-cyl dithiophosphatyl) 2,3-

epoxybutane,

1,4-bis-S-(0,0-dioctadecyl dithiophosphatyl) 2,3-thioepoxybutane,

1,4-bis-S-(0,0-dioctadecy-l dithiophosphatyl) 2,3-epoxybutane,

1,4 bis-S-(O,O-dinonadecyl dithiophosphatyl) 2,3-th'ioepoxybutane,

1,4-bis-S-(0,0-dinonadecyl-dithiophosphatyl) 2,3-

epoxybutane,

1,4-bis-S-(0,0-dieicosyl dithiophosphatyl) 2,3-thioepoxybutane,

1,4-1bis-S-(0,0-dieicosyl dithiophosphatyl) 2,3-epoxybutane, etc.

Here again, monoalkyldithiophosphates may be employed for reacting with 1,4-dichl0ro-2,3-epoxybutane Also, the

al-lcyl group or groups may be straight or branched chain.

It is understood that any Suitable haloepoxy compound may be used for reacting with the alkali metal dithiophosphate. In general, the haloepoxy compound will contain from :3 to 6 or more carbon atoms. Illustrative chloro-substi'tuted epoxides include epiohlorohydr-in, 1,2- epi 4 chl-orobutane, 2,3 epi 4 chlorobutane, 1,2- cpi 5 chloropentane, 2,3 epi 5 chloropentane, 1,2- epi 6 chlorohexane, 2,3 epi 6 chlorohexane, etc. Dichloro substituted epox ides include l,4-dichloro-2,3- epoxybutane, 1,5 dichl-oro 2,3 epoxypentane, 1,6- dichloro 2,3 epoxyhexane, 1,6 dichl0ro-3,4 epoxyhexane, etc. The chloro substituted compounds generally are preferred, although the bromo substituted compounds may be used. In still other cases, the corresponding iodo or fluoro substituted compounds may be employed.

As hereinbefore set forth, the preferred compounds comprise those in which R in the above general formula is an alkyl group and, in one embodiment, R also is an alkyl group. In another embodiment R 'and/ or R" may be selected from other hydrocarbon groups including valkylene, aryl, alkaryl, aralkyl, cycloalkyl, etc. Illustrative examples of such compounds include I-S-(O-heptadecenyl dithiophosphatyl) 2,3-th-ioepoxypropane,

1S-(Oheptadeoenyl dithiophosphatyl) 2,3-epoxypropane,

l-S-(0,0-dipentenyl dithiophosphatyl) 2,3-thioepoxypropane,

1-S-(0,0-dipentenyl ditbiophosphatyl) 2,3-epoxypropane,

1,4'bis-S-(O-pentadecenyl dith-iophosphatyl) 2,3-tl1ioepoxybutane,

1,4bis-S*(O-pentadeenyl dithiophosphatyl) 2,3-epoxybutane,

1,4-bis-S-(0,0-diheptenyl dithiophosphatyl) 2,3-thioepoxybutane,

1,4-biS-S- (OD-diheptenyl dithiophosphatyl) 2,3-epoxybutane, etc.,

1-S-'(O-phenyl dithio-phosphatyl) 2,3-thioepoxybu tane,

1-S-(O-phenyl dithiophosphaty'l) 2,3-epoxybutane,

1-S-(0,0-diphenyl dithiophosphatyl) 2,3-thioepoxypropane,

l-S-(0,0-diphenyl dithiophosphatyl) 2,3-epoxypropane,

1, 4-bis-S-(O-phenyl dithiophosphatyl) 2,3-thioepoxybutane,

1,4-bis-S-(O-phenyl dithiophosphatyl) 2,3-epoxybutane,

1,4-'bis-S-(0,0-diphenyl dithiophosphatyl) 2,3-t-hioepoxybutane,

1,4-bis-S-(0,0diphenyl dithiophosphatyl) 2,3-epoxybutane, etc.,

l-S-(O-xylyl dithiophosphatyl) 2,3-thioepoxypropane,

l-S-(O-xylyl dithiophosp-hatyl) 2,3-epoxypropane,

1S-(0,0-ditolyl dithiophosphatyl) 2,3-th'ioepoxy-propane,

1-S-(0,0-ditolyl dithiophosph-atyl) 2,3-epoxy-propane,

1,4-bis-S-(O-propylphenyl dithiophosphatyl) 2,3-thioepoxybutane,

1,4-bis-S (G-propylphenyl dithiophosphatyl) 2,3-epoxybutane,

1,4b-bis-S-(0,0-dixyly1 dithiophosphatyl) 2,3-thioepoxy- 1 utane,

1,4-bis-S-(0,0-dixyly-l dithiophosphatyl) 2,3-epoxybutane,

1,4-b'is-S-(O-ethylphenyl dithiophosphtayl) 2,3-thioepoxybutane,

1,4-biS-S-(O-ethylphenyl dithiophosphatyl) 2,3-epoxybutane,

-1,4bis-S-(0,0-ditolyl dit-hiophosphatyl) 2,3-thioepoxy butane,

1, 4abis-S-(0,0-ditolyl dithiophosphatyl) 2,3-epoxybutane, etc.,

l-S-(O-phenbutyl dithiophosphatyl) 2,3-thioepoxypropane,

1-S-(O-phenbutyl dit-hiophosphatyl) 2,3-epoxypropane,

1-S-(0,0-diphenethyl dithiophospha-tyl) 2,3-thioepoxypropane,

1-S-(0,0-diphenethyl dithiophosphatyl) 2,3-epoxypropane,

1,4-bis-S-(O-phenpropyl dithiophosphatyl) 2,3-thioepoxypropane,

1,4-bis-S-(O-phenpropy1 dithiophosphatyl) 2,3-epoxypropane,

1,4bis-S-(0,0-diphenethyl dithiophosphatyl) 2,3-thioepoxypr-opane, etc.,

l-S-(O-cyclohexyl dithiophosphatyl) 2,3-thioepoxypropane,

1-S-(O-cyclohexyl dit-hiophosphatyl) 2,3-epoxyprop ane,

'l-S-(Qo-dicyclopentyl dithiophosphatyl) 2,3nthi0- epoxypropane,

:1-S-'(0,0-dieyolopentyl dithiophosphatyl) 2,3-epoxypropane,

1,4-bis-S-(O-cyclohexyl dithiophosphatyl) 2,3-thioepoxybutane,

1,4-bis-S-(O-cyclohexy1 dithiophosphatyl) 2,3-epoxybutane,

1,4-bis-S (O-dicyclohexyl dithiophosphatyl) 2,3-t-hioepoxybutane,

1,4-bis-S-(O-dicyclohexyl dithiophosphatyl) 2,3-epoxybutane, etc.

However, it is understood that the various compounds which may be prepared in accordance with the present invention are not necessarily equivalent in the utility thereof in particular applications.

As hereinber'ore set forth, the novel compounds of the present invention are readily prepared by the reaction of an alkali metal dithiophosphate and a haloepoxide in the presence of the oxygen-containing polar solvent. When R" in the above general formula is a hydrocarbon group, the phosphate and haloepoxide are reacted in equal mol proportions. When R in the above general formula is a dithiophosphatyl group, two mol proportions of the dithiophosphate are reacted with one mol proportion of the haloepoxide. The reaction is readily effected by refluxing the reactants for a time suificient to accomplish the desired reaction. This may range from 0.5 to 48 hours or more and generally will be for a time of from about 3 to about 20 hours. The refluxing temperature generally will be within the range of from about 30 to about 150 C. and preferably about 50 to about C. The pressure may range from atmospheric to 1000 p.s.i.g. or more.

As hereinbefore set forth, it is essential that the reaction is effected in the presence of an oxygen-containing polar solvent. Any suitable oxygen-containing polar solvent is employed including alcohols, particularly methanol, ethanol, propanol, butanol, etc., ketones including acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, etc., and glycols, glycolethers, alkylamides, dimethylformamide, dirnethylacetamide, nitromethane, dimethyl or diethyl sulfoxide, dimethyl ether, diethyl ether, etc. When desired, either or both of the reactants may be prepared as a solution in the solvent for ease of handling or in forming a more fluid reaction mixture, or the solvent may be added to the reaction mixture. The solvent permits etlecting the reaction at lower temperature and thereby favors the formation of monomers. Polymers are formed at the higher temperatures. The polymers or polycondensates are not harmful in lubricating oils, but are undesirable in pesticidal and insecticidal formulations.

In one method of operation the haloepoxide and alkali metal dialkyldithiophosphate are formed as separate solutions in an alcoholic solvent. The solutions then are mixed, and the mixture is heated and maintained at refluxing conditions for the desired time. Following the completion of the reaction, the desired product is recovered in any suitable manner. In one method the product is dissolved in an aromatic solvent, washed with water and/or sodium bicarbonate or similar solution, dried over anhydrous sodium sulfate, anhydrous potassium carbonate or the like, and then filtered and heated to remove the aromatic solvent, the latter generally being effected under vacuum.

The compositions of this invention possess insecticidal properties with good inner-therapeutic action. They may be employed against many types of mites and insects such as, for example, Corausius larvae, Cotoneaster aphid, apple aphid, black bean aphid, aster aphid, green peach aphid, chrysanthemum aphid, pea aphid, etc. The compounds or mixture of these may be used for the control of various larvae, mites, eggs of mites and such insects as flour beetle, Mexican bean beetle, black carpet beetle, milkweed bug, German cockroaches, southern armyworms, mealy bug, sow bug, citrus red spider, greenhouse red spider, various mosquitoes, yellow fever mosquito, malarial mosquito, etc.

The novel composition of matter of the present invention is particularly useful as an additive to hydrocarbon oil and still more particularly to lubricating oil. In the latter oil, the compound serves a number of important functions such as oxidation inhibitor (peroxide decomposer), bearing corrosion inhibitor, ring anti-pluggin g additive, extreme pressure additive, pour point depressant, viscosity index improver, detergent, etc.

The lubricating oil may be straight mineral lubricating oil derived from parafiinic, naphthenic, asphaltic or mixed base petroleum crud-es or blends thereof and is generally highly refined. In another embodiment the lubricating oil is a synthetic lubricating oil and may be one or a mixture of various types including aliphatic esters, polyalkylene oxides, silicones, esters of phosphoric and silicic acids, highly fluorine-substituted hydrocarbons, etc. Of the aliphatic esters, di-(Z-ethylhexyl) sebacate is being used on a comparatively large commercial scale. Other aliphatic esters include dialkyl azelates, dialkyl suberates, dialkyl pimelates, dialkyl adipates, dialkyl glutarates, etc. Specific examples of these esters include dihexyl azelate, di-( Z-ethylhexyl) azelate, di-3,5,5-.trimethylhexyl glutarate, di 3,5,5 trimethylpentyl glutarate, di (2 ethylhexyl) pimeiate, di-(Z-ethylhexyl) adipate, tri-amyl tricarb- 'allylate, pentaerythritol tetracaproate, dipropylene glycol dipelargonate, 1,5 pentanediol di (Z-ethylhexanonate), etc. The polyalkylene oxides and derivatives include polyisopropylcne oxide, polyisopropylene oxide diether, polyisopropylene oxide diester, etc. The silicones include methyl silicone, methylphenyl silicone, etc., and the silicates include, for example, tetraisooctyl silicate, etc. Synthetic lubricants proposed for use in high temperature service as, for example, jet fuel lubrication are pentaerythritol esters and trimethylol propane esters.

The novel composition of the present invention also is useful as an additive to lubricating greases. These may be either of synthetic or petroleum origin. The synthetic greases generally are referred to as lithium base grease, sodium base grease, calcium base grease, barium base grease, strontium base grease, aluminum base grease, etc. These greases are solids or semi-solid gels and, in general, are prepared by the addition to mineral or synthetic lubricating oils of hydrocarbon-soluble metal soaps or salts of higher fatty acids as, for example, lithium stearate, calcium stearate, aluminum naphthenate, etc. The grease may contain thickening agents such as silica, carbon black polyacrylates, talc, etc. Another type of grease is prepared from oxidized petroleum wax, to which the saponifiable base is combined with the proper amount of the desired saponifying agent, and the resultant mixtures processed to produce a grease. Other types of greases in which the features of the present invention are usable include petroleum grease, Whale grease, Wool grease, etc., and those made from inedible fats, tallow, butchers waste, etc.

The novel composition also is useful in the stabilization of polyolefins and particularly polyethylene. The polyolefins preferably are of high molecular weight, usually having a molecular weight above 1000 and extending into the hundreds of thousands range. Generally, these are synthetically prepared. A typical exam le is the widely used polyethylene plastics. Other polyolefins include polypropenes, polybutenes, and polymers of higher molecular weight olefins. These may be of the high density, medium density, or low density type. Polyethylene is utilized, for example, as thermoplastic molding or coating agent. Because of its high dielectric strength and its resistance to water, polyethylene is particularly advantageous for use as insulators or dielectrics in condensers and other similar electronic equipment. However, polyethylene is subject to attack by atmospheric oxygen, particularly at elevated temperatures, either in use or during manufacture, and this impairs the desirable properties thereof including, for example, a reduction in the desirable electric properties, gelation upon oxidation, etc.

Other organic substances which deteriorate in storage, during treatment, and/ or in use, include hydrocarbons, and particularly motor fuels such as unsaturated gasoline, blends of unsaturated and saturated gasolines, etc., as well as jet fuel, diesel oil, mineral oil, fuel oil, residual oil, drying oil, waxes, resins, rubber, etc. These substances are adversely affected by oxygen, with the resultant formation of one or more of undesirable gum, sediment, discoloration, cracking, corrosion, and/or other deleterious reactions.

When used as an additive to organic substrates, the novel compounds of the present invention may be utilized in a concentration of from about 0.0001% to about 25% by weight of the organic substrate, although in some cases higher or lower concentrations may be employed. The exact concentration to be used will depend upon the particular substrate to be treated. In most cases concentrations from about 0.01% to about 2% by weight generally will be employed.

It is understood that the composition of the present invention may be used along with other additives incorporated in the organic substrate. For example, one or more of an additional additive including metal deactivator, dye, viscosity index improver, pour point depressant, antifoaming additive, lubricity and extreme pressure additive, anti-scuffing additive, detergent, corrosion inhibitor, etc., may be incorporated in the substrate. When desired, the composition of the present invention may be prepared as a mixture with one or more of these other additives and marketed and/or incorporated in the substrate in this manner. The composition of the present invention may be incorporated in the organic substrate in any suitable manner and at any suitable stage of preparation. When incorporated in a liquid substrate, the composition of matter is added thereto and intimately mixed by conventional means. When added to a solid or semi-solid substrate, the composition of the present invention preferably is added during the manufacture thereof in order to obtain intimate mixing. For example, in the manufacture of grease, the composition of the present invention may be added to one or more of the components of the grease prior to compositing and processing thereof, or it may be added to the mix at any time, preferably before final processing in order to obtain intimate mixing and dissolving thereof in the grease. In other cases, the solid substrate may be dipped, soaked or immersed in the additive, or the latter may be sprayed, brushed or otherwise applied to the solid substrate.

The following examples are introduced to illustrate further the novelty and utility of the present invention but not with the intention of unduly limiting the same.

EXAMPLE I 1-S-(0,0-diisopropyl dithiophosphatyl) 2,3-thioepoxypropane and 1-S-(0,0-diisopropyl dithiophosphatyl) 2,3- epoxypropane were prepared as follows: 126 g. of potassium diisopropyl dithiophosphate were dissolved in 200 g. of Formula 30 alcohol ethanol-10% methanol). The solution was heated to refluxing temperature and 50.6

g. of epichlorohydrin were added drop-wise while mixing and refluxing for 14 hours. The product then was filtered to remove white crystalline potassium chloride, dissolved in benzene, washed with water, sodium bicarbonate solution, again with water, and finally dried over anhydrous potassium carbonate. The benzene was evaporated by heating on a steam bath under water pump vacuum. The product is a mixture of 1-S-(0,0-diisopropyl dithiophosphatyl) 2,3-thioepoxypropane and 1-S-(0,0-diisopropyl dithiophosphatyl) 2,3-epoxypropane and was recovered in a yield of 103 g. as a fluid light amber liquid, having a refractive index n of 1.5180.

the percent potassium would be of the order of 13.6% by weight.

EXAMPLE III As hereinbefore set forth, the product is a mixture of Table l the thioepoxypropane and epoxypropane derivatives. This was determined by sulfur and phosphorus analysis. Run Number 1 2 3 The theoretical and actual percents sulfur and phosphorus for the above product are shown below, as well as the Add'f Y 05 7 0.5 %i1ltsyf l 1V8 1 one weig \VGlg 0 ratio of sulfur to phosphorus. Exaniple I Example II product product Percent gggggf Bearing wt. loss, grus 2.0021 0. 0027 0. 0049 Oil ring plugging, percent" 5 0 0 (ileorsillmptiommL/hrnn 6.03 5.23 10. 49

S80 12 Theory Found Theory Found Theory Found Neutralization N0 1078 0'87 0'68 gapoznificatiori bNlo, MgKOtH/gm. Thioepog-yalkane en a1 1e mso u es, percen derivative 33.5 10.8 3.1 SUS at 265 285 100 F 742 388 377 Epoxymkane 210F 74.7 57.6 56.7

derivative. 23. 65 11. 2. 07

From the data in the above table, it will be noted that From the above, it will be seen that the ratio of sulfur t 30 the novel Compounds of the Present invention were y phosphorus found is 2.85, which is in between the and 2.07 ratios for the thioepoxyalkane and epoxyalkane derivatives. Accordingly, the product is a mixture of both of these derivatives. GLC (gas-liquid chrornotographic) analysis of the crude product showed that 77% thereof was one compound, which, from the above data, indicates that it is l-S-(0,0-diisopropyl dithiophosphatyl) 2,3-thioepoxypropane.

As hereinbefore set forth, the reaction involves the formation of potassium chloride. The above product also was analyzed for potassium and was found to contain only 0.012% by weight of potassium. In contrast, if the potassium were retained in the final product, the percent potassium would be of the order of 13.6% by weight. This further confirms the chemical formula of the product as hereinbefore set forth.

EXAMPLE II 1,4-bis-S-(0,0-diisopropyl dithiophosphaltyl) 2,3-thioepoxybutane and 1,4-bis-S-(0,0-diisopropyl dithiophosphatyl) 2,3-epoxybutane were prepared as follows: 138 g- (0.5 mol plus 12 g.) of potassium diisopropyl dithiophosphate were dissolved in 200 g. of refluxing methanol. 35.25 g. (0.25 mols) of 1,4-dichloro-2,3-epoxybutane were dissolved in 20 g. of methanol and the resultant solution was added drop-wise to the refluxing solution of potassium diisopropyl dithiophosphate. Refluxing was continued for .six hours, after which the reaction mixture was allowed to cool, toluene solvent added and then washed three times with water, dried over anhydrous sodium sulfate, filtered, and the toluene removed by heating on a steam bath under water pump vacuum. The product is a mixture of 1,4-bis-S-(0,0-diisopropyl dithiophosphatyl) 2,3-thioepoxybutane and 1,4-bis-S-(0,0-diisopropyl dit-hiophosphatyl) 2,3-epoxybutane and was recovered in a yield of 87 g. as a reddish brown oily liquid, having an index of refraction .4 1.5278.

Here again, sulfur and phosphorus analyses indicate that the product predominates in 1,4-bis-S-(0,0-diisopropyl dithiophosphatyl) 2,3-thioepoxybutane and that the product also contains l,4-bisS-(0,0-diisopropyl dithiophosphatyl) 2,3-epoxybutane.

The product also was analyzed for potassium concentration and it was found to :be only 0.016% by weight. Again, if potassium were retained in the final product,

effective in reducing corrosion, as evidenced by the very low bearing weight loss as compared to Run No. 1 made in the absence of the additive. Also, the compounds were effective in preventing undesired changes in the lubricating oil, as evidenced by the neutralization number, saponification number, percent pentane insolubles and viscosities. EXAMPLE IV l-S-(QO-ditridecyl dithiophosphatyl) 2,3-thioepoxy propane and I-S-(QO-ditridecyl dithiophosphatyl) 2,3- epoxy-propane were prepared as follows: g. of ditri- 1 ecyl dithiophosphate were reacted with 19.5 g. of potassium hydroxide dissolved in 200 g. of Formula 30 alcohol, following which 30 g. of epichlorohydrin were added dropwise, while refluxing for 13 hours. The reaction mixture was cooled, dissolved in benzene, Washed twice with water, dried over anhydrous sodium sulfate, filtered and the benzene removed by distilling on a steam bath under vacuum. The product is a mixture of 1-S (0,0-ditridecyl dithiophosphatyl) 2,3-thioepoxypropane and 1-S-(0,0-ditridecyl dithiophosphatyl) 2,3-epoxypropane and was recovered in a yield of greater than g. as an amber colored liquid, having an index of refraction n of 1.48815.

EXAMPLE V l-S'(O-stearyl-O-Z-ethylbutyl dithiophosphatyl) 2,3- thioepoxypr-opane and 1-S-(O-stearyl-O-Z-ethyl-butyl dithiophosphatyl) 2,3-epoxypropane were prepared .by r acting 114.6 g. of O-stearyl-O-Z-ethylbutyl dithiophosphoric acid with 8 g. of sodium hydroxide to form the sodium salt and then reacting the sodium salt with 18.5 g. of epichlorohydrin in the presence of 200 g. of methanol. The reaction mixture was refluxed for 3 hours. Sodium chloride was filtered oil and the product worked-up in th manner hereinbefore described.

When evaluated in the Lauson engine as described in Example III, the oil containing one-half percent by weight of the above additive resulted in a bearing weight loss of 0.0625, 0% oil ring plugging and oil consumption of 5.97 nil/hr. All parts were free.

EXAMPLE VI 1-S-(0,0-diethyl dithiophosphatyl) 2,3-thioepoxypropane and 1-S-(0,0-diethyl dithiophosphatyl) 2,3-epox3- propane are prepared as follows: 98 g. of potassium diethyl dithiophosphate are dissolved in 200 g. of methanol. The solution is heated to refluxing temperature and 25 g. of epichlorohydrin are added drop-wise while mixing and refluxing for 10 hours. The product then is liltered to remove crystalline potassium chloride, dissolved in benzene, washed with water, dried over anhydrous sodium nitrate, and the benzene is evaporated on a steam bath under water vacuum. The product is recovered as a fluid light amber liquid.

EXAMPLE VII 1,4-bis S (0,0-diethyl dithiophosphatyl) 2,3-thioepoxybutane and 1-4-bis-S-(0,0-diethyl dithiophosphatyl) 2,3epoxybutane are prepared as follows: 110 g. (0.5 mol plus 12 g.) of potassium diethyl di'thiophosphate is dissolved in 206 g. of Ir'luLlXlIlg Formula 30 alcohol. 35.25 g. (0.25 mols) of 1,4-dichloro 2,3-epoxybutane are dissolved in 20 g. of Formula 30 alcohol and the resultant solution is added drop-wise to the refluxing solution of potassium die-thyl dithiophosphate. Refiuxing is continued for six hours, after which the mixture is filtered to remove crystalline potassium chloride, toluene solvent is added and then washed three times with water, dried over anhydrous sodium sulfate and the toluene removed by heating on a steam bath under water pump vacuum. The product is recovered as a reddish brown oily liquid.

EXAMPLE VH1 I-S-(O-heptadecenyl dithiophosphatyl) 2,3-thioepoxypropane and I-S-(O-heptadecenyl dithiophosphatyl) 2,3- epoxypropane are prepared by reacting equal moi proportions of heptadecenyl dithiophosphate sodium salt with epichlorohydrin. Each of the reactants are formed as separate solutions in alcohol solvent. The dithiophosphate sodium salt solution is heated to refluxing temperature and the epichlorohydrin is gradually added thereto. The refluxing is continued for 8 hours, after which the reaction mixture is allowed to cool and the desired product recovered by washing, filtering and distillation under vacuum to remove entrained solvent.

'liAMPLE IX 1,4-bis-S-(0,0-ditolyl dithiophosphatyl) 2,3-thioeooxybutane and 1,4-bis-S-(0,0-ditolyl dithiophosphatyl) 2,3- epoxybutane are prepared by reacting 2 molar proportions of ditolyl dithiophosphate with 1 molar proportion of 1,4-dibromo-2,3-epoxybutane. The reaction is effected in substantially the same manner as hereinbet'ore set forth and the desired product is recovered by washing, filtering and vacuum distillation to remove entrained solvent.

EXAMPLE X 1,4-bis-S- 0,0-dicyclohexyl clithiophosphatyl) 2,3 -thioepoxypentane and 1,4-bis-S-(0,0-dicyclohexyl dithiophosphatyl) 2,3-epoxypentane are prepared by reacting 2 :51: molar proportions of dicyciohexyl dithiophosphate with 1 molar proportion of l,S-dicl1loro--2,B-epoxypentane. The reaction is effected in substantially the same manner as hereinbefore set forth and the desired product is recovered by washing, filtering and distilling under vacuum to remove entrained solvent.

1 claim as my invention:

1. Hydrocarbon material normally subject to oxidative deterioration containing, as an inhibitor therefor from about 0.000l% to about 25 by weight of an S-dithiophosphatyl compound selected from the group consisting of S-dithiophosphatyl thioepoxyalkane and S-dithiophosphatyl epoxyalkane.

2. Lubricating oil containing from about 0.000l% to about 25% by weight of an S-dithiophosphatyl compound selected from the group consisting of S-dithiophosphatyl thioepoxyalirane and S-dithiophosphatyl epoxyalkane.

3. Lubricating oil containing from about 0.0001% to about 25% by Weight of l-S-(G,O-diall yl dithiophosphatyl) 2,3-thioepoxyallzane.

4-. Lubricating oil containing from about 0.0001% to about 25% by weight of 1,4bis-(O-alkyl dithiophosphatyl) 2,3-thioepoxyalkane.

5. Lubricating oil containing from about 0,6001% to about 25% by weight of 1-S-(0,0-diall yl dithiophosphatyl) 2,3-epoxyalkane.

6. Lubricating oil containing from about 0.000l% to about 25% by Weight of 1,4-bis-(O-alkyl dithiophosphatyl) 2,3-epoxyalkane.

'7. Lubricating oil containing from about 0.000175 to about 25 by weight of l--S-(0,0-ditridecyl dithiophosphatyl) 2,3-thioepoxypropane.

8. Grease containing from about 0.000l% to about 25% by weight of an S-dithiophosphatyl compound selected from the group consisting of S-dithiophosphatyl thioepoxyalkane and S dithiophosphatyl epoxyalkane.

9. Polyolefin containing from about till-001% to about 25 by Weight of an S-dithiophosphatyl compound selected from the group consisting of S-dithiophosphatyl thioepoxyalkane and S-dithiophosphatyl epoxyananc.

References Cited by the Examiner UN lTED STATES PATENTS 2,565,920 8/51 Hook et al. 252-466 2,627,521 2/53 Coover 260-457 2,856,369 10/58 Smith et a1. 25246.6 X

2,895,983 7/59 Assert 252 :6.6 X

3,004,996 10/61 Arakelian et a1. 25246.6

FOREIGN PATENTS 1,082,915 6/60 Germany.

DANEEL E. WY MAN, Primary Examiner. 

1. HYDROCARBON MATERIAL NORMALLY SUBJECT TO OXIDATIVE DETERIORATION CONTAINING, AS AN INHIBITOR THEREFOR FROM ABOUT 0.0001% TO ABOUT 25% BY WEIGHT OF AN S-DITHIOPHOSPHATYL COMPOUND SELECTED FROM THE GROUP CONSISTING OF S-DITHIOPHOSPHATYL THIOEPOXYALKANE AND S-DITHIOPHOSPHATYL EPOXYALKANE. 